Ruthenium-phosphine complex

ABSTRACT

A ruthenium-phosphine complex is disclosed, which is represented by formula (I): 
     
         [Ru(R-BINAP)MCl.sub.k ].sub.l X.sub.m                      (I) 
    
     wherein R-BINAP represents a tertiary phosphine represented by formula (II): ##STR1## wherein R represents hydrogen atom or methyl group; M represents Zn, Al, Ti, or Sn; X represents N(C 2  H 5 ) 3  or CH 3  CO 2  ; in the case that X represents N(C 2  H 5 ) 3 , l is 2 and m is 1, and when M represents Zn, then k is 4, when M represents Al, then k is 5, and when M represents Ti or Sn, then k is 6; and in the case that X represents CH 3  CO 2 , l is 1 and m is 2, and when M represents Zn, then k is 2, when M represents Al, then k is 3, and when M represents Ti or Sn, then k is 4.

FIELD OF THE INVENTION

The present invention relates to a ruthenium-phosphine complex useful asa catalyst for various organic synthesis reactions, particularlyasymmetric hydrogenation reaction.

BACKGROUND OF THE INVENTION

Hitherto, a number of transition metal complexes have been used ascatalysts for organic synthesis reactions. In particular, since noblemetal complexes are stable and easy in handling though they areexpensive, there have been reported a number of synthesis researchesusing them as catalysts. In particular, there have been a number ofreports on asymmetric catalysts used in asymmetric syntheses, i.e.,asymmetric isomerization reaction or asymmetric hydrogenation reaction.Among them, especially metal complexes formed between metallic rhodiumand an optically active tertiary phosphine are well known as catalystsfor the asymmetric hydrogenation reaction. Such complexes typicallyinclude a rhodium-phosphine catalyst using2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (hereinafter abbreviated as"BINAP") as a ligand as disclosed in JP-A-55-61937. (The term "JP-A" asused herein means an "unexamined published Japanese patentapplication".).

On the other hand, known ruthenium complexes, though there are not somany reports as compared with rhodium complexes, include those havingBINAP or 2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl (hereinafterabbreviated as "T-BINAP") as a ligand, e.g., Ru₂ Cl₄ (BINAP)₂ (NEt₃)(wherein Et represents an ethyl group, hereinafter the same) and Ru₂ Cl₄(T-BINAP)₂ (NEt₃), as reported in Ikariya et al., J. Chem. Soc., Chem.Commun., pp. 922 (1985). Further, asymmetric hydrogenation reactions ofallyl alcohol and of isoquinoline-type alkaloid using Ru(CH₃ CO₂)(BINAP)as a ruthenium complex are reported in Noyori et al., J. Am. Chem. Soc.,109, pp. 1596 (1987) and ibid., 108, pp. 7117 (1986), respectively.Moreover, [Ru(BINAP)]X₂ (wherein X represents ClO₄, BF₆, or PF₆) isreported in H. Takaya et al., J. Org. Chem., 52, pp. 3174-3176 (1987)However, the state-of-the-art ruthenium complexes are not satisfactoryin catalytic activity as well as durability.

Although metallic rhodium is a metal for excellent complex catalysts, itis limited in terms of place and quantity of production and isexpensive. When used as a catalyst, it forms a large proportion in costof the product, ultimately resulting in increase in cost of the finalcommercial products. While metallic ruthenium is cheaper than rhodiumand appears promising as a catalyst for industrial application, it stillhas problems in its activity to cope with precision reactions and itsrange of application. Therefore, it has been keenly demanded to developa catalyst which is inexpensive, has high activity and durability, andcatalyzes asymmetric reactions to attain high optical yields, i.e., toproduce reaction products having high optical purity.

As a result of extensive investigations with the purpose of meeting theabove-described industrial demand, the inventors have discovered a novelruthenium complex having high catalytic activity, which is usable eitherfor general syntheses when the ligand thereof is optically inactive orfor asymmetric syntheses when the ligand thereof is optically active.The present invention has been completed based on this finding.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a ruthenium-phosphinecomplex represented by formula (I):

    [Ru(R-BINAP)MCl.sub.k ].sub.l X.sub.m                      ( 1)

wherein R-BINAP represents a tertiary phosphine represented by formula(II): ##STR2## wherein R represents hydrogen atom or methyl group; Mrepresents Zn, Al, Ti, or Sn; X represents N(C₂ H₅)₃ or CH₃ CO₂ ; in thecase that X represents N(C₂ H₅)₃, l is 2 and m is 1, and when Mrepresents Zn, then k is 4, when M represents Al, then k is 5, and whenM represents Ti or Sn, then k is 6; and in the case that X representsCH₃ CO₂, l is 1 and m is 2, and when M represents Zn, then k is 2, whenM represents Al, then k is 3, and when M represents Ti or Sn, then k is4.

DETAILED DESCRIPTION OF THE INVENTION

The novel ruthenium-phosphine complex (I) according to the presentinvention can be produced by using Ru₂ Cl₄ (R-BINAP)₂ NEt₃ or Ru(CH₃CO₂)₂ (R-BINAP) as a starting material.

The starting material, Ru₂ Cl₄ (R-BINAP)NEt₃, can be obtained by themethods as disclosed in Ikariya et al., J. Chem. Soc., Chem. Commun.,pp. 922 (1985) and JP-A-61-63690. That is, it can be obtained byreacting 1 mol of [RuCl₂ (COD)]_(n) (wherein COD representscycloocta-1,5-diene, hereinafter the same), which is obtainable fromreaction between ruthenium chloride and COD, with 1.2 mols of R-BINAP ina solvent (e.g., toluene or ethanol) in the presence of 4 mols oftriethylamine under heating.

The thus-obtained Ru₂ Cl₄ (R-BINAP)₂ NEt₃ is reacted with one member ofLewis acids selected from zinc chloride, aluminum chloride, titaniumtetrachloride, and tin tetrachloride in a solvent such as methylenechloride at a temperature of from 10° to 25° C. for a period of from 2to 20 hours. Thereafter, the solvent is distilled off, and the residueis evaporated to dryness, whereby the ruthenium-phosphine complexaccording to the present invention can be obtained.

Another starting material, Ru(CH₃ CO₂)₂ (R-BINAP), can be obtained bythe method proposed by the inventors in European patent No. 245,959A.That is, Ru₂ Cl₄ (R-BINAP)₂ NEt₃ as a starting material, which isobtained by the method as described above, is reacted with sodiumacetate in an alcoholic solvent (e.g., methanol, ethanol, and t-butanol)at a temperature of from about 20° to 110° C. for a period of from 3 to15 hours. Thereafter, the solvent is distilled off, and the desiredcomplex is extracted with a solvent (e.g., diethyl ether or ethanol) andthen evaporated to dryness to obtain a crude complex. The crude complexis further recrystallized from a solvent (e.g., ethyl acetate) to obtaina purified product.

The thus-obtained Ru(CH₃ CO₂)2(R-BINAP) is reacted with one member ofthe above-described Lewis acids in a solvent such as methylene chlorideat a temperature of from 10° to 25° C. for a period of from 2 to 20hours. Thereafter, the solvent is distilled off, and the residue isevaporated to dryness, whereby the ruthenium-phosphine complex accordingto the present invention can be obtained.

In the foregoing production methods, if optically active R-BINAP isused, there can be obtained the ruthenium-phosphine complex of thepresent invention having the corresponding optical activity.

The thus-obtained ruthenium-phosphine complex according to the presentinvention has excellent properties as a catalyst for asymmetrichydrogenation reaction, etc. For example, in the asymmetrichydrogenation of enamides, e.g.,(Z)-N-acyl-1-(4-methoxyphenyl-methylene)-3,4,5,6,7,8-hexahydroisoquinoline,with respect to an Ru(CH₃ CO₂)₂ (BINAP) complex reported in The ChemicalSociety of Japan, Spring Annual Meeting, ZlllL43, dated April 2, 1986,though the optical yield is high as 98% ee, the catalytic activity is100 in terms of substrate/catalyst ratio. On the other hand, theruthenium-phosphine complex according to the present invention exhibitsextremely high catalytic activity so that the reaction smoothly proceedswith the complex having a concentration of from 1/300 to 1/2000 mol permol of the substrate and that a hydrogenation product formed therefromprovides a desired product at a selectivity reaching nearly 100%.Further, the thus-produced amide has an optical purity of from 90 to95%. Thus, the ruthenium-phosphine complex according to the presentinvention shows very excellent results as industrially useful catalysts.

Next, the present invention is described in detail with reference to thefollowing Examples and Use Examples, but the present invention is notlimited thereto.

EXAMPLE 1

Synthesis of [Ru((-)-T-BINAP)SnCl₆ ]₂ NEt₃(bis[ruthenium-(2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl)-hexachlorotin]-triethylamine):

Into a 80 ml Schlenk's tube was charged 0.52 g (0.3 mmol) of Ru₂ Cl₄((-)-T-BINAP)2NEt3 After thoroughly purging the Schlenk's tube withnitrogen, 20 ml of methylene chloride and 0.16 g (0.6 mmol) of SnCl₄were added thereto, and the mixture was stirred at room temperature for15 hours. After completion of the reaction, the methylene chloride wasdistilled off under reduced pressure, and the residue was evaporated todryness to obtain 0.68 g of dark brown [Ru((-)-T-BINAP)SnCl₆ ]₂ NEt₃.The yield was 100%. Elemental analysis for C₁₀₂ H₉₅ Cl₁₂ NP₄ Sn₂ Ru₂ :

    ______________________________________                                                   P    C          H      Cl                                          ______________________________________                                        Found (%)    5.91   53.48      4.36 17.56                                     Calcd. (%)   5.33   52.72      4.12 18.31                                     ______________________________________                                    

The instrumental analysis values are as follows. That is, the ³¹ Pnuclear magnetic resonance (hereinafter abbreviated as "³¹ P NMR")spectrum was measured using a Model AM400 apparatus (a product of BrukerInc.) at 161 MHz, with the chemical shifts being measured with 85%phosphoric acid used as an external standard. ³¹ P NMR (CDCl₃)δppm:14.14 (d, J=41.7 Hz); 62.57 (d, J=41.7 Hz)

EXAMPLE 2

Synthesis of [Ru((-)-BINAP)AlCl₃ ](CH₃ CO₂)₂([ruthenium-(2,2'-diphenylphosphino)-1,1'-binaphthyl)trichloroaluminum]-diacetate):

Into a 80 ml Schlenk's tube was charged 0.63 g (0.75 mmol) of Ru(CH₃CO₂)2((-)-BINAP). After thoroughly purging the Schlenk's tube withnitrogen, 10 ml of methylene chloride was added thereto for dissolution.Separately, 0.1 g (0.75 mmol) of AlCl₃ was charged into a 80 mlSchlenk's tube, and 20 ml of methylene chloride and the above-preparedmethylene chloride solution of Ru(CH₃ CO₂)₂ ((-)-BINAP) weresuccessively added thereto, followed by stirring the mixture for 15hours. After completion of the reaction, the methylene chloride wasdistilled off under reduced pressure, and the residue was evaporated todryness to obtain 0.73 g of dark brown [Ru((-)-BINAP)AlCl₃ ](CH₃ CO₂)₂.The yield was 100%. Elemental analysis for C₄₈ H₃₈ O₄ P₂ Cl₃ AlRu:

    ______________________________________                                                   P    C          H      Cl                                          ______________________________________                                        Found (%)    6.17   60.07      4.38 11.16                                     Calcd. (%)   6.35   59.12      3.93 10.60                                     ______________________________________                                    

³¹ P NMR (CDCl₃)δppm: 14.16 (d, J=41.5 Hz); 62.56 (d, J=41.5 Hz)

EXAMPLES 3 TO 16

In Examples 3 to 9, complexes were synthesized in the same manner as inExample 1 except that the types of the starting R-BINAP and Lewis acidwere changed; and in Examples 10 to 16, complexes were synthesized inthe same manner as in Example 2 except that the types of the startingR-BINAP and Lewis acid were changed.

The analysis values of the thus-obtained complexes are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    Example                                                                            Compound of the Invention                                                                         Elemental Analysis Value (%)                         No.  (Molecular Formula) Element                                                                             Found                                                                              Calcd.                                                                            .sup.31 P NMR (δ ppm)           __________________________________________________________________________    3    [Ru((-)-BINAP)ZnCl.sub.4 ].sub.2 NEt.sub.3                                                        P     6.82 6.31                                                                              14.15 (d, J = 41.6 Hz)                                         C     56.94                                                                              57.51                                                                             62.58 (d, J = 41.6 Hz)                                         H     4.61 4.06                                           C.sub.94 H.sub.79 Cl.sub.8 NP.sub.4 Zn.sub.2 Ru.sub.2                                             Cl    13.79                                                                              14.45                                     4    [Ru((-)-BINAP)AlCl.sub.5 ].sub.2 NEt.sub.3                                                        P     6.77 6.33                                                                              14.17 (d, J = 41.5 Hz)                                         C     56.70                                                                              57.69                                                                             62.57 (d, J = 41.5 Hz)                                         H     4.36 4.07                                           C.sub.94 H.sub.79 Cl.sub.10 NP.sub.4 Al.sub.2 Ru.sub.2                                            Cl    17.62                                                                              18.11                                     5    [Ru((-)-BINAP)TiCl.sub.6 ].sub.2 NEt.sub.3                                                        P     6.61 5.99                                                                              14.17 (d, J = 41.4 Hz)                                         C     54.23                                                                              54.54                                                                             62.57 (d, J = 41.4 Hz)                                         H     4.35 3.85                                           C.sub.94 H.sub.79 Cl.sub.12 NP.sub.4 Ti.sub.2 Ru.sub.2                                            Cl    19.21                                                                              20.55                                     6    [Ru((-)-BINAP)SnCl.sub.6 ].sub.2 NEt.sub.3                                                        P     6.20 5.60                                                                              14.19 (d, J = 41.3 Hz)                                         C     50.71                                                                              51.05                                                                             62.57 (d, J = 41.3 Hz)                                         H     3.95 3.60                                           C.sub.94 H.sub.79 Cl.sub.12 NP.sub.4 Sn.sub.2 Ru.sub.2                                            Cl    18.78                                                                              19.24                                     7    [Ru((-)-T-BINAP)ZnCl.sub.4 ].sub.2 NEt.sub.3                                                      P     6.16 5.97                                                                              14.15 (d, J = 41.6 Hz)                                         C     58.31                                                                              59.03                                                                             62.59 (d, J = 41.6 Hz)                                         H     5.07 4.61                                           C.sub.102 H.sub.95 Cl.sub.8 NP.sub.4 Zn.sub.2 Ru.sub.2                                            Cl    13.25                                                                              13.67                                     8    [Ru((-)-T-BINAP)AlCl.sub.5 ].sub.2 NEt.sub.3                                                      P     6.27 5.99                                                                              14.16 (d, J = 41.5 Hz)                                         C     58.45                                                                              59.20                                                                             62.58 (d, J = 41.5 Hz)                                         H     4.99 4.63                                           C.sub.102 H.sub.95 Cl.sub.10 NP.sub.4 Al.sub.2 Ru.sub.2                                           Cl    16.54                                                                              17.13                                     9    [Ru((-)-T-BINAP)TiCl.sub.6 ].sub.2 NEt.sub.3                                                      P     5.91 5.68                                                                              14.15 (d, J = 41.6 Hz)                                         C     55.72                                                                              56.14                                                                             62.57 (d, J = 41.6 Hz)                                         H     4.76 4.39                                           C.sub.102 H.sub.95 Cl.sub.12 NP.sub.4 Ti.sub.2 Ru.sub.2                                           Cl    19.19                                                                              19.50                                     10   [Ru((-)-BINAP)ZnCl.sub.2 ](CH.sub.3 CO.sub.2).sub.2                                               P     6.48 6.33                                                                              14.15 (d, J = 41.5 Hz)                                         C     58.22                                                                              58.94                                                                             62.57 (d, J = 41.5 Hz)                                         H     3.67 3.92                                           C.sub.48 H.sub.38 Cl.sub.2 O.sub.4 P.sub.2 ZnRu                                                   Cl    6.88 7.25                                      11   [Ru((-)-BINAP)SnCl.sub.4 ](CH.sub.3 CO.sub.2).sub.2                                               P     5.97 5.62                                                                              14.14 (d, J = 41.5 Hz)                                         C     53.04                                                                              52.30                                                                             62.59 (d, J = 41.5 Hz)                                         H     4.11 3.47                                           C.sub.48 H.sub.38 Cl.sub.4 O.sub.4 P.sub.2 SnRu                                                   Cl    13.40                                                                              12.86                                     12   [Ru((-)-BINAP)TiCl.sub.4 ](CH.sub.3 CO.sub.2).sub.2                                               P     5.73 6.00                                                                              14.15 (d, J = 41.6 Hz)                                         C     56.52                                                                              55.89                                                                             62.58 (d, J = 41.6 Hz)                                         H     4.18 3.71                                           C.sub.48 H.sub.38 Cl.sub.4 O.sub.4 P.sub.2 TiRu                                                   Cl    13.92                                                                              13.75                                     13   [Ru((-)-T-BINAP)ZnCl.sub.2 ](CH.sub.3 CO.sub.2).sub.2                                             P     5.63 5.99                                                                              14.13 (d, J = 41.7 Hz)                                         C     61.21                                                                              60.39                                                                             62.57 (d, J = 41.7 Hz)                                         H     4.87 4.48                                           C.sub.52 H.sub.46 Cl.sub.2 O.sub.4 P.sub.2 ZnRu                                                   Cl    7.31 6.86                                      14   [Ru((-)-T-BINAP)AlCl.sub.3 ](CH.sub.3 CO.sub.2).sub.2                                             P     5.76 6.01                                                                              14.14 (d, J = 41.4 Hz)                                         C     61.23                                                                              60.56                                                                             62.55 (d, J = 41.4 Hz)                                         H     5.08 4.50                                           C.sub.52 H.sub.46 Cl.sub.3 O.sub.4 P.sub.2 AlRu                                                   Cl    10.66                                                                              10.31                                     15   [Ru((-)-T-BINAP)SnCl.sub.4 ](CH.sub.3 CO.sub.2).sub.2                                             P     5.21 5.35                                                                              14.16 (d, J = 41.3 Hz)                                         C     54.46                                                                              53.91                                                                             62.57 (d, J = 41.3 Hz)                                         H     4.81 4.00                                           C.sub.52 H.sub.46 Cl.sub.4 O.sub.4 P.sub.2 SnRu                                                   Cl    12.64                                                                              12.24                                     16   [Ru((-)-T-BINAP)TiCl.sub.4 ](CH.sub.3 CO.sub.2).sub.2                                             P     5.54 5.70                                                                              14.14 (d, J = 41.5 Hz)                                         C     57.81                                                                              57.42                                                                             62.58 (d, J = 41.5 Hz)                                         H     4.94 4.26                                           C.sub.52 H.sub.46 Cl.sub.4 O.sub.4 P.sub.2 TiRu                                                   Cl    13.61                                                                              13.04                                     __________________________________________________________________________

USE EXAMPLE 1

Asymmetric hydrogenation of(Z)-N-formyl-1-(4-methoxyphenylmethylene)-3,4,5,6,7,8hexahydroisoquinoline: ##STR3##

Into a Schlenk's tube which had previously been dried and purged withargon was weighed and charged 18.8 mg (0.0081 mmol) of[Ru((-)-T-BINAP)SnCl₆ ]₂ NEt₃ as a catalyst. Then, 40 ml of degassedanhydrous methanol was added thereto, and the solution was stirred inthe presence of hydrogen at room temperature for 2 hours. Separately, asolution of 516 mg (1.82 mmols) of(Z)-N-formyl-1-(4-methoxyphenylmethylene)-3,4,5,6,7,8-hexahydroisoquinolineadded to 20 ml of degassed anhydrous methanol was prepared. A fractionof 4.30 ml (molar ratio of substrate/catalyst =1000/1) was taken fromthe catalyst solution and mixed with a substrate solution. The mixturewas transferred into an autoclave and stirred at 75° C. for 47 hoursunder a hydrogen pressure of 35 kg/cm². After completion of thestirring, the reaction mixture was concentrated under reduced pressureand purified by silica gel column chromatography to obtain 520 mg of(+)-N-formyl-1-(4-methoxyphenylmethylene)-1,2,3,4,5,6,7,8-octahydroisoquinoline.The yield was 100%.

[α]_(D) ²⁵ +22.6 (c=1.17, methanol)

After deformylation, the product was reacted with2,3,4,6-tetra-O-acetyl-β-O-glycopyranosyl isocyanate and then subjectedto reversed phase HPLC analysis to determine the optical yield. Thus,the optical yield was found to be 98% ee.

The respective spectral data are given below.

¹ H NMR (400 MHz, CDCl₃)δ ppm: 1.68 (m, 4H), 1.90 (m, 4H), 2.20 (m, 2H),2.64 (dd, J=10.4, 13.9 Hz, 0.6H), 2.90 (m, 2.4H), 3.31 (dd, J=6.6, 12.9Hz, 0.4H), 3.58 (d, J=9.9 Hz, 0.6H), 3.77 (s, 3H), 4.37 (dd, J=6.7, 12.9Hz, 0.6H), 4.68 (broad s, 0.4H), 6.80 (m, 2H), 6.99 (m, 0.6H), 7.05 (m,0.4H), 7.39 (s, 0.6H), 7.92 (s, 0.4H)

¹³ C NMR (100 MHz, CDCl₃)δ ppm: 22.7, 22.8, 22.9, 27.7, 29.7, 30.0,30.8, 33.4, 36.3, 37.6, 40.4, 53.2, 55.2, 60.4, 60.8, 113.6, 114.1,127.77, 127.84, 128.9, 129.8, 130.0, 130.2, 130.4, 158.2, 158.4, 160.8,161.1

UV (CH₃ OH) nm: 220, 277, 284

MS: m/e 285

USE EXAMPLES 2 TO 16

Using each of the ruthenium-phosphine complexes obtained in Examples 2to 16, the asymmetric hydrogenation reaction of(Z)-N-formyl-1-(4-methoxyphenylmethylene)-3,4,5,6,7,8-hexahydroisoquinoline was carried out in the same reactionprocedures as in Use Example 1 to produce(+)-N-formyl-1-(4-methoxyphenylmethylene)-1,2,3,4,5,6,7,8-octahydroisoquinoline.The results are shown in table 2.

                                      TABLE 2                                     __________________________________________________________________________    Use                      Substrate/  Tempera-                                                                              Conver-                                                                            Optical                     Example                  Catalyst                                                                            Hydrogen                                                                            ture Time                                                                             sion Yield                       No.  Compound of the Invention                                                                         (mol/mol)                                                                           (kg/cm.sup.2)                                                                       (°C.)                                                                       (hr)                                                                             (%)  (% ee)                      __________________________________________________________________________    2    [Ru((-)-BINAP)ZnCl.sub.4 ].sub.2 NEt.sub.3                                                        500   50    55   50 90   97                          3    [Ru((-)-BINAP)AlCl.sub.5 ].sub.2 NEt.sub.3                                                        1000  50    55   30 95   97                          4    [Ru((-)-BINAP)SnCl.sub.6 ].sub.2 NEt.sub.3                                                        1000  35    75   25 98   98                          5    [Ru((-)-BINAP)TiCl.sub.6 ].sub.2 NEt.sub.3                                                        1000  50    55   40 92   95                          6    [Ru((-)-T-BINAP)ZnCl.sub.4 ].sub.2 NEt.sub.3                                                      500   50    55   48 91   96                          7    [Ru((-)-T-BINAP)AlCl.sub.5 ].sub.2 NEt.sub.3                                                      1000  50    75   28 93   97                          8    [Ru((-)-T-BINAP)TiCl.sub.6 ].sub.2 NEt.sub.3                                                      1000  50    55   39 91   97                          9    [Ru((-)-BINAP)ZnCl.sub.2 ](CH.sub.3 CO.sub.2).sub.2                                               300   50    55   47 85   94                          10   [Ru((-)-BINAP)AlCl.sub.3 ](CH.sub.3 CO.sub.2).sub.2                                               1000  50    65   32 91   94                          11   [Ru((-)-BINAP)SnCl.sub.4 ](CH.sub.3 CO.sub.2).sub.2                                               1000  50    75   23 93   96                          12   [Ru((-)-BINAP)TiCl.sub.4 ](CH.sub.3 CO.sub.2).sub.2                                               500   50    55   38 89   95                          13   [Ru((-)-T-BINAP)ZnCl.sub.2 ](CH.sub.3 CO.sub.2).sub.2                                             300   50    55   48 87   93                          14   [Ru((-)-T-BINAP)AlCl.sub.3 ](CH.sub.3 CO.sub.2).sub.2                                             1000  50    75   29 90   94                          15   [Ru((-)-T-BINAP)SnCl.sub.4 ](CH.sub.3 CO.sub.2).sub.2                                             1000  50    75   24 92   97                          16   [Ru((-)-T-BINAP)TiCl.sub.4 ](CH.sub.3 CO.sub.2).sub.2                                             500   50    55   41 88   95                          __________________________________________________________________________

The present invention is to provide a novel ruthenium-phosphine complex.This complex exhibits excellent properties as a catalyst for variousorganic synthesis reactions, particularly asymmetric hydrogenationreaction and shows industrially superior results with respect toselective hydrogenation of olefins and catalytic activity. Further, thecomplex can be produced with a low production cost as compared with theconventional rhodium-based catalysts, leading to a contribution to areduction in product price. Thus, the invention is of industrially greatvalue.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A ruthenium-phosphine complex of formula (I):

    [Ru(R-BINAP)Cl.sub.k M].sub.m X.sub.n                      (I)

wherein R-BINAP is a tertiary phosphate of formula (II): ##STR4##wherein R is the same and is hydrogen atom or methyl group; M is a Lewisacid selected from ZnCl₂, AlCl₃, TiCl₄, and SnCl₄ ; X is N(C₂ H₅)₃ orCH₃ CO₂ ; in the same case that X is N(C₂ H₅)₃, then k is 2, m is 2, andn is 1; and in the case that X CH₃ CO₂, then k is 0, m is 1, and n is 2.2. A ruthenium-phosphine complex of formula (III):

    [Ru(R-BINAP)Cl.sub.2 M].sub.2 N(C.sub.2 H.sub.5).sub.3     (III)

wherein R-BINAP is a tertiary phosphine of formula (II): ##STR5##wherein R is the same and is hydrogen atom or methyl group; and M is aLewis acid selected from ZnCl₂, AlCl₃, TiCl₄, and SnCl₄.
 3. Aruthenium-phosphine complex of formula (III):

    [Ru(R-BINAP)Cl.sub.2 M].sub.2 N(C.sub.2 H.sub.5).sub.3     (III)

wherein R-BINAP is a tertiary phosphine of formula (II): ##STR6##wherein R is the same and is hydrogen atom or methyl group; and M is aLewis acid selected from ZnCl₂, AICl₃, TiCl₄, and SnCl₄, obtained byreacting Ru₂ Cl_(h) (R-BINAP)₂ N(C₂ H₅)₃, wherein R-BINAP is the same asdefined above, with a Lewis acid selected from ZnCl₂, AlCl₃, TiCl₄, andSnCl₄ in an inert solvent at from 10° to 25° C.
 4. A ruthenium-phosphinecomplex of formula (IV):

    [Ru(R-BINAP)M](CH.sub.3 CO.sub.2).sub.2                    (IV)

wherein R-BINAP is a tertiary phosphine of formula (II): ##STR7##wherein R is the same and is hydrogen atom or methyl group; and M is aLewis acid selected from ZnCl₂, AlCl₃, TiCl₄, and SnCl₄.
 5. Aruthenium-phosphine complex of formula (IV):

    [Ru(R-BINAP)M](CH.sub.3 CO.sub.2).sub.2                    (IV)

wherein R-BINAP is a tertiary phosphine of formula (II): ##STR8##wherein R is the same and is hydrogen atom or methyl group; and M is aLewis acid selected from ZnCl₂, AlCl₃, TiCl₄, and SnCl₄, obtained byreacting Ru(CH₃ CO₂)₂ (R-BINAP), wherein R-BINAP is the same as definedabove, with a Lewis acid selected from ZnCl₂, AlCL₃, TiCl₄, and SnCl₄ inan inert solvent at from 10° to 25° C.